Process of making sulfur dyes.



UNITED STATES ALOIDE FRANCOIS POIRRIER, OF PARIS, FRANCE.

PROCESS OF MAKING SULFUR DYES.

SPECIFICATION forming part of Letters Patent No. 648,597,

dated May .1 1 900.

Application filed May 16,1899. Serial No. 717,037. (No specimens.)

' fication is a full, clear, and exact description.

Sulfureted coloring-matters have been produced by causing sulfur or sulfur and sodium sulfid to react on hydroxylated, amido hydroxylated, polyam'ido, amidoacetylated,

and aromatic compounds. I have since found that the application of this reaction to mix: tures of aromatic compounds of different nature leads to unexpectedresults essentially different from those obta'ined'by treating the compounds separately. Thus if mixtures, for instance, of paramidophenoland alphanaphthol, or of paramidophenol and orthophenylenediamin, or of paramidophenol and triamidobenzene are treated the coloringmatters obtained are different in tint and in chemical properties from the coloring-matters obtained from paramidophenol, or alphanaphthol, or orthophenylenediamin, or triamidobenzene when any one of these is treated alone. The coloring-matter from paramidophenol is readily soluble in free alkalies or carbonates and dyes cotton black. The coloring-matters from orthophenylenediamin and triamidobenzene are insoluble in alkaline carbonates. The coloring-matters from alpha-naphthol, orthophenylenediamin, and triamidobenzene dye cotton brown-red, while the coloring-matters above referred to are clear black and insoluble or scarcely soluble in alkaline carbonates, but are all soluble in alkali sulfids.

' Example I: There are heated to 200 centigrade for three hours in an iron pan one part of paramidophenol, 1.2 parts of alphanaphthol, and three parts of sulfur. The whole is allowed to cool and has added to it eight parts of crystallized sodium sulfid. It is then gradually heated up and kept for three to four hours at a temperature of about180 to 200 centigrade. The brittle black mass thus obtained dissolves in alkalies or alkali sulfids. It dyes a clearer black than the coloring-matter derivedfrom paramidophenol treated by itself, and,as is known,alpha-naphthol gives a weak brown coloring-matter. In

this example nitroso-alpha-naphthols and their reduction products can be substituted for the alpha-naphthol.

Example II: Into 2.5 parts of sulfur-fused and heated to about 100 centigrade are introduced one part of paramidophenol and 1.15 parts of orthonitranilin. The mixture is heated for two hours to 180 to 200 centigrade. There are then added eight to ten parts of. crystallized sodium sulfid, and the heat is kept for three to four hours at 180 to 210 centigrade. The product, which is scarcely at all soluble in alkaline carbonates,

gives a black dye more clear than the product obtained by treating pai amidophenol alone. For the orthonitranilin may be substituted orthophenylenediamin, and the position ofthe substitutions may be inverted. Thus in one of the aromatic nuclei of the substances treated the two substitutions of am in and phenol into para in one of them and amin alone into ortho in the other might be amin and phenol into ortho in the one and amiu into para in the other-that is tosay, para- Y phenyldiamin may be substituted for paramidophenol and orthoamidophenol for orthophenylenediamin.

' Example III: One part of paramidophenol and one part of triamidobenzene-1z3z4 (or a corresponding quantity of one of its salts set free by soda) are heated with two parts of sulfur, the temperature being raised to 200 centigrade and kept up for two to three hours. Eight parts of crystallized sodium sulfid are then made to act on the above, the temperature being maintained for three to four hours from 190 to 220 centigrade. The coloringmatter thus obtained is insoluble in alkaline carbonates and dyes cotton black. For the triamidobenzene-1z3z4 may be substituted chrysoidin from anilin, triamidobenzene- 1:2: 6, dinitranilins-1z2z4 and -1: 2: 6, or the Bismarck brown from metaphenylenediamin. As in example II, the arrangement of the substitution may also be inverted. For paramido phenol may be substituted paraphenylenediamin and for triamidobenzene dinitrophenol or diamidophenol.

In the three examples for the paramidophenol may be substituted any substance capable of producing it in the reaction medium, such as azo derivatives of phenol, paranitrophenol, nitrosophenol, oxyazobenzene, &c. The methods of operating may also be varied. Thus the heating may be first with sulfur and then with sodium sulfid, or with both together. The temperatures maybe at first very high or may be gradually raised to 180, 210, or 220 centigrade.

All the coloring-matters obtained, as above .set forth, may be applied without any further preparation or they may be freed fromaccessory substances which they contain by washing with acidulated boiling water, and the residue constituting the coloring-matter may be prepared for dyeing by bruising it with sodium sulfid or other solvent.

These coloring-matters all dye cotton clear black in an alkaline bath with or without addition of sodium sulfid. The shades obtained on exposureto the air rapidly become very intense. Contrary to those obtained from paramidophenol, they give without bichromate treatment stable and definite shades having great resistance to alkaline washing.

WVhile reference is made in the following claims to paramidophenol as one of the substances forming part of the mixture of aromatic compounds, its equivalentssuch as the azo derivatives of phenol, paranitrophe- 1101, and the like-may be employed with analogous results, and likewise, while reference is made toalpha-naphthol as the other substance forming part of the mixture, its equivalentsorthonitranilin, orthophenylenediamin, and

triamidobenzene-may be employed with of paramidophenol and alpha-naphthol, said coloring-matter being clear black, insoluble or scarcely soluble in alkaline carbonates, but soluble in alkali sulfids.

4. The herein-described coloringmatter formed by causing sulfurand sodium sulfid to react on a mixture of paramidophenol and alpha-naphthol, said coloring-matter being clear black, insoluble or scarcely soluble in sulfids. 1

In witness whereof I have hereunto signed my name in thepresence of two subscribing witnesses.

ALCIDE FRANCOIS POIRRIER.

Vitnesses:

J U'LES ARMENGAUD, J eune,

J. ALLISON BOWEN.

-alkalinecarbonates, but soluble in alkali 

